WO1999005151A1 - Produits solides poreux a base de 1,3,5-benzenetricarboxylate et d'ions metalliques - Google Patents

Produits solides poreux a base de 1,3,5-benzenetricarboxylate et d'ions metalliques Download PDF

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Publication number
WO1999005151A1
WO1999005151A1 PCT/GB1998/002213 GB9802213W WO9905151A1 WO 1999005151 A1 WO1999005151 A1 WO 1999005151A1 GB 9802213 W GB9802213 W GB 9802213W WO 9905151 A1 WO9905151 A1 WO 9905151A1
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WO
WIPO (PCT)
Prior art keywords
solid product
btc
chiral
pyr
benzenetricarboxylate
Prior art date
Application number
PCT/GB1998/002213
Other languages
English (en)
Inventor
Cameron John Kepert
Matthew Jonathan Rosseinsky
Original Assignee
Isis Innovation Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GBGB9715825.7A external-priority patent/GB9715825D0/en
Priority claimed from GBGB9801726.2A external-priority patent/GB9801726D0/en
Application filed by Isis Innovation Limited filed Critical Isis Innovation Limited
Priority to EP98935211A priority Critical patent/EP1001960A1/fr
Priority to JP2000504146A priority patent/JP2001510845A/ja
Priority to US09/463,818 priority patent/US6372932B1/en
Publication of WO1999005151A1 publication Critical patent/WO1999005151A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/04—Nickel compounds
    • C07F15/045—Nickel compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/06—Cobalt compounds
    • C07F15/065—Cobalt compounds without a metal-carbon linkage

Definitions

  • This invention relates to solid products which are both porous and chiral, by virtue of an absence of symmetry of a crystal structure of the atoms and molecules with its mirror image, involving reflection or inversion.
  • porous chiral solids The search for porous chiral solids is driven largely by a desire to perform enantioselective separations and syntheses, processes which are of fundamental importance to the pharmaceuticals industry.
  • Solid materials currently used to perform enantioseparations include natural and synthetic polymers, chiral sorbents and chiral membranes.
  • Parallel with the search for solids is the synthesis of solution species for homogeneous catalysis and molecular recognition.
  • a solid product which is a porous chiral (10, 3)-a network of 1 ,3,5- benzenetricarboxylate molecules
  • the solid product is an infinite molecular coordination network.
  • the compounds described below are the only known infinite molecular coordination networks to be both chiral and porous, and are among only a handful of solids known to have both of these properties. These solid products contain three metal atoms for every two 1 ,3,5- benzenetricarboxylate molecules.
  • the groups X may be the same or different at different locations of the molecule.
  • the nature of the group X is not specially critical. Preferably they are inert groups small enough not to cause steric hindrance such as lower (C ⁇ Cs) aliphatic groups or I, Br, Cl or F or particularly hydrogen atoms.
  • each metal atom acts as a linear connector between two 1 ,3,5-benzenetricarboxylate molecules.
  • the metal is a transition or lanthanide metal having a coordination greater than 2.
  • each metal atom (linking two 1 ,3,5-benzenethcarboxylate molecules) also carries one or more coordinated ligands.
  • ligands may be mono- or poly-dentate, and promising examples include alcohols, thiols, water, ammonia, aliphatic and aromatic amines and amides, halides, carboxylates, oxalate, nitrate, nitrite, sulfate, phosphate, oxide, sulfide, cyanide and thiocyanate.
  • desolvated salts obtained by heating it is not essential for all coordination sites of the metal atom to be satisfied by a coordinating ligand.
  • the metal atoms should preferably carry additional ligands that favour the linear coordination of the 1 ,3,5-benzenetricarboxylate and which satisfy the coordination environment of the metal.
  • additional ligands that favour the linear coordination of the 1 ,3,5-benzenetricarboxylate and which satisfy the coordination environment of the metal.
  • the solid product When the metal has an oxidation state of 2, and these ligands are not electrically charged, then the solid product is electrically neutral. Alternatively if the metal atoms are in an oxidation state greater than or less than 2; and/or one or more of the ligands is electrically charged, then the whole molecular coordination network may be cationic or anionic. This may confer useful properties as described in more detail below.
  • the solid product may consist of four (10, 3)-a networks.
  • the solid product may consist of less than four such interpenetrating networks, and this may increase the solvent accessible volume of the product.
  • the solid product of the invention may be made by providing a solution of a metal salt, e.g. a transition or lanthanide metal salt, and a 1 ,3,5-benzenetricarboxylate as defined above, in a solvent consisting of one or more ligands for the chosen metal.
  • a metal salt e.g. a transition or lanthanide metal salt
  • a 1 ,3,5-benzenetricarboxylate as defined above
  • the solution contains substantially three metal atoms for every two 1 ,3,5-benzenetricarboxylate molecules (btc).
  • the desired product is recovered as a crystalline solid from the solution. Although each crystal is enantiomerically pure, the polycrystalline product may be a racemic mixture of crystals.
  • an enantiomerically pure product it may be preferable to make an enantiomerically pure product, and this may be achieved either by using a chiral ligand for the metal, by forming the solid about a chiral template, by seeding crystal growth from a single enantiomeric crystal, by crystallising in the presence of a chiral cosolute, or by selective nucleation on a chiral surface.
  • Porous framework solids have several chemical uses, ranging from heterogeneous catalysis to molecular (neutral molecule, cation or anion) recognition and exchange.
  • chiral (10, 3)-a network materials of btc include use
  • FIG. 1 shows part of the structure of compound (A).
  • a nickel atom 10 acts as a linear connector between two btc molecules 12, 14. Other coordination positions of the nickel atom are occupied by two molecules of pyridine 16 and two molecules of ethylene glycol 18. It is believed that the whole structure may be stabilised by hydrogen bonds 20 formed between an oxygen atom of a btc molecule and an oxygen atom of ethylene glycol.
  • Figure 2 shows a (10, 3)-a network structure involving btc molecules 12,14 connected by nickel atoms 10.
  • Figures 3(a) and 3(b) show the two enantiomers of the (10,3)-a network structure of Figure 2.
  • a new structural form of a porous chiral solid has been discovered, in which two distorted (10,3)-a networks interpenetrate.
  • the networks are constructed by a 2:3 mixture of 1 ,3,5-benzenetricarboxylate anions and metal ions, such that the two of the former coordinates approximately linearly through one of the latter, and each of the carboxylate groups binds to a metal.
  • the (10,3)-a networks are topologically the same as those seen in materials A1 , A2, A3, A4 and A5 (Example 1 ), although here the networks are distorted due to the coordinated nickel atoms lying out of the plane of the anion's benzene plane.
  • This solid contains only two (rather than four) interpenetrating (10,3)-a networks.
  • the material has quite a different cavity structure to A1 - A5, even though it is similar in many ways to the other salts: two btc anions are connected linearly through a Ni" cation, and the axial coordination sites of the metal are occupied by pyridine and alcohol (in the case of Figures 5 - 8, 1 ,2-propanediol) ligands.
  • the chirality of the framework material is coupled to the chirality of the alcohol that is coordinated to the metal (as determined by single crystal X-ray diffractometry).
  • Enantiomerically pure (homochiral) samples of B may therefore be synthesised by using optically resolved diols.
  • FIG. 1 shows part of the structure of compound B1.
  • a nickel atom 10 acts as a linear connector between two btc molecules 12, 14. Other coordination positions of the nickel atom are occupied by two molecules of pyridine 16 and one molecule of the bidentate (doubly coordinating) 1 ,2-propanediol molecule 18. It is believed that the whole structure is stabilised by hydrogen bonds 20 formed between oxygen atoms of the btc anion and alcoholic hydrogen atoms of the 1 ,2-propanediol.
  • Figure 6 shows a doubly-interpenetrating (10,3)-a network structure involving btc molecules 12, 14 connected by nickel atoms 10. The terminal ligands of the metal centres are omitted for clarity.
  • Figure 7 shows a single distorted (10,3)-a network: linear connectors represent metal atoms and triangular connectors represent 1 ,3,5-benzenetricarboxylate anions.
  • Figure 8 is a conceptual view of a solid product of the invention consisting of two interpenetrating networks of the kind shown in Figure 7.
  • the solvent-filled cavities within the structure may therefore be varied systematically, the choice of ligands around the metal centre greatly influencing their chemical nature. With a potentially limitless number of arrays possible, it is expected that the cavities could be fine-tuned for very specific inclusion selectivities. Further important variations include
  • metal cations act as linear-connectors for the trigonal 1 ,3,5-benzenetricarboxylate anion.
  • the distance between neighbouring btc units is too small to allow the interpenetration of networks of opposite chirality.
  • the relatively short molecular repeat distance of coordinated btc (ca. 10 A) therefore dictates that (10, 3)- a network solids of this anion be chiral.
  • Solids of the (10,3)-a backbone may be synthesised enantiomerically pure by the coordination of a chiral ligand to the metal atom. Further methods of homochiral synthesis that offer great promise are selective nucleation at a chiral surface, seeding of crystal growth, use of a chiral molecular template, and crystallisation in the presence of a chiral cosolute. Separation of crystal according to their optical rotation may also become viable, since large transparent single crystals may be grown readily.
  • Single crystals of A1, A2, A3 and A4 were grown by slow diffusion of pyridine into a stoichiometric 2:3 solution of trimesic acid (1 ,3,5- benzenetricarboxylic acid) and Ni(NO 3 ) 2 .6H 2 O in ethylene glycol (A1) or methanol (A2) or ethanol (A3) or n-propanol (A4).
  • Single crystals of A5 were grown by slow diffusion of pyridine into a stoichiometric 2:3 solution of trimeric acid and Co(NO 3 ) 2 .6H 2 O in ethylene glycol.
  • Diffusion techniques include the use of a) H-shaped cells, where the reactants diffuse toward one another through the horizontal arm of the vessel (useful when the solutions of the reactants are denser than the diffusion medium), b) test-tubes, where the reactants diffuse toward one another vertically (useful when the reactants are alternately more and less dense than the diffusion medium), c) non-aqueous gels based on tetramethoxysilane, where the species in solution diffuse towards one another in a U-tube or test-tube.
  • Single crystals of A1 were placed in Lindemann capillaries and mounted both on an Enraf-Nonius DIP2000 diffractometer equipped with graphite-monochromated Mo-K ⁇ radiation, a nitrogen gas cryostream and Eu/Ba image plate detectors, and on an Enraf-Nonius MACH3 diffractometer equipped with Cu-K ⁇ , radiation and a scintillation point detector.
  • Structural refinement data were collected at 150 K with Mo-K ⁇ and at 295 K with Cu-K ⁇ radiation.
  • MACH3 diffractometer a single quadrant of data was collected.
  • Elemental analysis of A1 , A2 and A3 indicates their composition.
  • Compound A1 is Ni(btc) 2/3 (pyr) 2 (eg) 2 .(eg) x (H 2 O) y where x « 1 and y « 1.3
  • Compound A2 is Ni(btc) 2/3 (pyr) 2 (MeOH) 2 .(MeOH) x (H 2 O) y where x « 2 and y « 1
  • compound A3 (see below) is Ni(btc) 2/3 (pyr) 2 (EtOH) 2 .(EtOH) x (H 2 O) y where x * 1.5 and y « 1 .
  • Single crystals of B1 and B2 were coated in an inert fluorinated oil, mounted on fine mohair fibres, and cooled rapidly to 150 K on an Enraf-Nonius DIP2000 diffractometer.
  • the diffractometer was equipped with graphite-monochromated Mo-K ⁇ radiation, a nitrogen gas cryostream operating at 150 K, and Eu/Ba image plate detectors.
  • Structural refinement data were collected at 150 K, reduced with the HKL suite of programs, and processed with the programs SHELXS-86 and
  • Peak indexing was achieved using the program DRAGON, and the unit cell parameters were refined using the program REFCEL.

Abstract

L'invention concerne un produit solide qui se présente sous la forme d'un réseau chiral poreux (10, 3)-a de molécules de 1,3,5-benzènetricarboxylate représenté par la formule (I), dans laquelle X est H, hydrocarbure, halogénure, etc. Ces molécules sont reliées par des atomes de métaux qui, de préférence, sont des atomes de métaux de transition ou des lanthanides comportant un ou plusieurs ligands coordonnés, comme par exemple des diols, et de préférence des ligands chiraux présents sous forme énantiomorphe pure.
PCT/GB1998/002213 1997-07-25 1998-07-24 Produits solides poreux a base de 1,3,5-benzenetricarboxylate et d'ions metalliques WO1999005151A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP98935211A EP1001960A1 (fr) 1997-07-25 1998-07-24 Produits solides poreux a base de 1,3,5-benzenetricarboxylate et d'ions metalliques
JP2000504146A JP2001510845A (ja) 1997-07-25 1998-07-24 １，３，５−ベンゼントリカルボキシレート及び金属イオンの多孔性固型物
US09/463,818 US6372932B1 (en) 1997-07-25 1998-07-24 Porous solid products of 1,3,5-benzenetricarboxylate and metal ions

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GBGB9715825.7A GB9715825D0 (en) 1997-07-25 1997-07-25 Porous solid products
GB9715825.7 1998-01-27
GBGB9801726.2A GB9801726D0 (en) 1998-01-27 1998-01-27 Porous solid products
GB9801726.2 1998-01-27

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WO2002068430A1 (fr) * 2001-02-23 2002-09-06 University Of South Florida Polyedre
WO2002070526A1 (fr) * 2001-03-08 2002-09-12 Basf Aktiengesellschaft Materiaux de structure organometalliques et leur procede de production
WO2002088148A1 (fr) * 2001-04-30 2002-11-07 The Regents Of The University Of Michigan Structures organometalliques isoreticulaires, procede d'obtention, et conception systematique du calibre des pores et fonctionnalites integrees, avec application pour le stockage des gaz
US6491740B1 (en) * 1999-07-22 2002-12-10 The Boc Group, Inc. Metallo-organic polymers for gas separation and purification
WO2003102000A1 (fr) * 2002-05-30 2003-12-11 Basf Aktiengesellschaft Corps formes contenant des structures organometalliques
WO2007023119A1 (fr) * 2005-08-22 2007-03-01 Basf Aktiengesellschaft Materiau mesoporeux a structure organometallique
US7582798B2 (en) 2004-10-22 2009-09-01 The Regents Of The University Of Michigan Covalently linked organic frameworks and polyhedra
US7652132B2 (en) 2003-05-09 2010-01-26 The Regents Of The University Of Michigan Implementation of a strategy for achieving extraordinary levels of surface area and porosity in crystals
US7662746B2 (en) 2005-04-07 2010-02-16 The Regents Of The University Of Michigan High gas adsorption metal-organic framework
US7799120B2 (en) 2005-09-26 2010-09-21 The Regents Of The University Of Michigan Metal-organic frameworks with exceptionally high capacity for storage of carbon dioxide at room-temperature
US8314245B2 (en) 2006-02-28 2012-11-20 The Regents Of The University Of Michigan Preparation of functionalized zeolitic frameworks
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DE102013202517A1 (de) 2013-02-15 2014-08-21 Universität Zu Köln Monokalium-2fluorbenzol-1,3,5-tricarboxylat
WO2015142954A1 (fr) * 2014-03-18 2015-09-24 The Regents Of The University Of California Réseaux métallo-organiques caractérisés en ce qu'ils comportent un grand nombre de sites d'adsorption par unité de volume
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US10058855B2 (en) 2015-05-14 2018-08-28 The Regents Of The University Of California Redox-active metal-organic frameworks for the catalytic oxidation of hydrocarbons
US10087205B2 (en) 2014-03-28 2018-10-02 The Regents Of The University Of California Metal organic frameworks comprising a plurality of SBUS with different metal ions and/or a plurality of organic linking ligands with different functional groups
US10118877B2 (en) 2014-12-03 2018-11-06 The Regents Of The University Of California Metal-organic frameworks for aromatic hydrocarbon separations
US10287304B2 (en) 2014-02-19 2019-05-14 The Regents Of The University Of California Acid, solvent, and thermal resistant metal-organic frameworks
US10494386B2 (en) 2014-03-18 2019-12-03 The Regents Of The University Of California Mesoscopic materials comprised of ordered superlattices of microporous metal-organic frameworks
US10597408B2 (en) 2015-11-27 2020-03-24 The Regents Of The University Of California Covalent organic frameworks with a woven structure
EP3763726A1 (fr) 2019-07-08 2021-01-13 3B Pharmaceuticals GmbH Composés comprenant un ligand de protéine d'activation de fibroblastes et leur utilisation
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US7652132B2 (en) 2003-05-09 2010-01-26 The Regents Of The University Of Michigan Implementation of a strategy for achieving extraordinary levels of surface area and porosity in crystals
US7582798B2 (en) 2004-10-22 2009-09-01 The Regents Of The University Of Michigan Covalently linked organic frameworks and polyhedra
US7662746B2 (en) 2005-04-07 2010-02-16 The Regents Of The University Of Michigan High gas adsorption metal-organic framework
US7842827B2 (en) 2005-08-22 2010-11-30 Basf Aktiengesellschaft Mesoporous metal-organic framework
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US7799120B2 (en) 2005-09-26 2010-09-21 The Regents Of The University Of Michigan Metal-organic frameworks with exceptionally high capacity for storage of carbon dioxide at room-temperature
US8314245B2 (en) 2006-02-28 2012-11-20 The Regents Of The University Of Michigan Preparation of functionalized zeolitic frameworks
US8809546B2 (en) 2006-02-28 2014-08-19 The Regents Of The University Of California Preparation of functionalized zeolitic frameworks
US9978474B2 (en) 2010-09-27 2018-05-22 The Regents Of The University Of California Conductive open frameworks
DE102013202524A1 (de) 2013-02-15 2014-08-21 Universität Zu Köln Monokalium-2,4,6-trifluorbenzol-1,3,5-tricarboxylat
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US10035127B2 (en) 2013-11-04 2018-07-31 The Regents Of The University Of California Metal-organic frameworks with a high density of highly charged exposed metal cation sites
US10287304B2 (en) 2014-02-19 2019-05-14 The Regents Of The University Of California Acid, solvent, and thermal resistant metal-organic frameworks
WO2015142954A1 (fr) * 2014-03-18 2015-09-24 The Regents Of The University Of California Réseaux métallo-organiques caractérisés en ce qu'ils comportent un grand nombre de sites d'adsorption par unité de volume
US10494386B2 (en) 2014-03-18 2019-12-03 The Regents Of The University Of California Mesoscopic materials comprised of ordered superlattices of microporous metal-organic frameworks
US10087205B2 (en) 2014-03-28 2018-10-02 The Regents Of The University Of California Metal organic frameworks comprising a plurality of SBUS with different metal ions and/or a plurality of organic linking ligands with different functional groups
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US10058855B2 (en) 2015-05-14 2018-08-28 The Regents Of The University Of California Redox-active metal-organic frameworks for the catalytic oxidation of hydrocarbons
US10597408B2 (en) 2015-11-27 2020-03-24 The Regents Of The University Of California Covalent organic frameworks with a woven structure
EP3763726A1 (fr) 2019-07-08 2021-01-13 3B Pharmaceuticals GmbH Composés comprenant un ligand de protéine d'activation de fibroblastes et leur utilisation
CN116023676A (zh) * 2023-02-28 2023-04-28 中国科学院赣江创新研究院 一种稀土基金属有机骨架材料的制备方法及其形貌调控方法
CN116023676B (zh) * 2023-02-28 2024-01-30 中国科学院赣江创新研究院 一种稀土基金属有机骨架材料的制备方法及其形貌调控方法

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